Nanocrystalline titanium dioxide (TiO2) was synthesized in microemulsions by using cetyltrimethylammonium bromide (CTAB) as surfactant. In order to investigate the crystal transformation and photoactivity at low temperature, the as-prepared precipitates were aged at 65°C or calcined at various temperatures. Analyses using powder X-ray diffraction (XRD) and Fourier transform infrared microscopy (FT-IR) showed that precursors without aging or calcination were noncrystal and adsorbed by surfactant. After aging for 6 h, the amorphous TiO2 began to change into anatase. The obtained catalysts, which were synthesized in microemulsions with weight ratios of n-hexanol/CTAB/water as 6 : 3 : 1 and calcined at 500°C, presented the highest photocatalytic degradation rate on methyl orange (MO), while the catalysts, which were aged at 65°C for 90 h, also exhibited an outstanding photocatalytic performance and a little higher than that of the commercial titania photocatalyst Degussa P25.